US4880842A - Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein - Google Patents
Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein Download PDFInfo
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- US4880842A US4880842A US07/197,063 US19706388A US4880842A US 4880842 A US4880842 A US 4880842A US 19706388 A US19706388 A US 19706388A US 4880842 A US4880842 A US 4880842A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09D157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C09D201/08—Carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
Definitions
- This invention relates to multi-stage polymer particles containing void space(s) therein which are useful as binding or opacifying agents in coating, impregnating and molding compositions.
- Core-shell polymer particles are disclosed in U.S. Pat. No. 4,427,836.
- the polymer particles of the '836 patent are prepared by sequentially emulsion polymerizing a core monomer system comprising monoethylenically unsaturated monomers, one of which has a carboxylic acid group and said carboxylic acid group containing monomer comprising at least 5% by weight of the core monomer system, polymerizing in the presence of the core polymer dispersion a shell monomer system which is permeable to aqueous volatile base selected from ammonia and amines, and neutralizing with ammonia or amine so as to swell said core and form particles which, when dried, contain a single void and cause opacity in compositions in which they are contained.
- the '836 patent requires that the carboxylic acid be present in the core in a polymeric form.
- the composition of the shell polymer is such as to be not permeable to fixed or permanent base according to said patent "so that films deposited from aqueous coating compositions comprising a volatile base-swollen core of the core/sheath polymer upon drying and resultant (at least partial) removal by volatilization of the base are not damaged by any permanent base present in the substrate coated or in solutions used later for cleaning the films.” (Column 3, ines 35-41).
- suitable swelling agents for acid-containing cores are ammonia, ammonium hydroxide, or a volatile lower aliphatic amine, such as trimethylamine, and triethylamine.
- suitable swelling agents for acid-containing cores are ammonia, ammonium hydroxide, or a volatile lower aliphatic amine, such as trimethylamine, and triethylamine.
- U.S. Pat. No. 4,468,498 discloses core-shell polymers having a core of polymeric acid and being swellable by a volatile base.
- U.S. Pat. No. 4,594,363 discloses a process for making core-shell polymer particles similar to the '836 patent, except that a fixed or permanent base is used to swell the particles.
- the '363 patent also requires that the core be polymerized from at least 5% by weight of acid-functional monomer.
- U.S. Pat. No. 4,469,825 discloses core-shell polymers having cores which are swellable by acid. High levels of copolymerized acid in the core polymer result in several disadvantages.
- One such disadvantage is that the acidic copolymers are polar and do not adsorb surfactants well, thus making them unstable and prone to coagulation or aggregaton into larger particle.
- Another disadvantage is that the acidic core polymers have a high affinity for water. This affinity makes it difficult to encapsulate the core with the shell polymer because he core tends to remain at the polymer-water interface on the surface of the composite particle.
- the present invention eliminates the instability, coagulation and encapsulation problems of polymers having relatively high levels of copolymerized acid in the core.
- swellable, multi-stage polymer particles can be prepared by introducing a non-polymeric carboxylic acid to an earlier stage of the particles.
- introducing a non-polymeric acid to an earlier stage after polymerization of said earlier stage preferably after polymerization of the complete, multi-stage polymer
- applicants have overcome the disadvantages of the core-shell polymers containing copolymerized acid in the core.
- This invention relates to opacifying, multi-stage polymer particles containing non-polymeric acid absorbed in an earlier stage and a process for making the polymer particles.
- the process comprises:
- each of said polymer stages is emulsion-polymerized from a monomer system comprising one or more ethylenically-unsaturated monomer(s) containing one or more --HC ⁇ C ⁇ group(s);
- the final polymer stage of said particles has a glass transition temperature of about 50° C. or greater;
- At least one low-acid polymer stage, other than said final polymer stage, is prepared from a monomer system containing less than about 5% by weight of monomers containing carboxylic acid functionality;
- each polymer stage is different from any adjacent polymer stage by either about a one percent difference by weight in the amount of any ethylenically unsaturated monomer used therein or by a difference in number average molecular weight between said stage and said adjacent stage of at least about a factor of 2;
- the polymer stages of said particles having a glass transition temperature of about 50° C. or greater comprise at least about 60% by weight of said particles;
- the polymer particles are useful as binders, opacifying agents and encapsulants.
- the present invention involves multi-stage polymer particles containing void space(s) within said particles which are useful as binders, opacifiers in paint and coatings, and as encapsulants for chemically or biologically-active materials.
- the polymer particles are prepared by:
- each of said polymer stages is emulsion-polymerized from a monomer system comprising one or more ethylenically-unsaturated monomer(s) containing one or more --HC ⁇ C ⁇ group(s);
- the final polymer stage of said particles has a glass transition temperature of about 50° C. or greater;
- At least one low-acid polymer stage, other than said final polymer stage, is prepared from a monomer system containing less than about 5% by weight of monomers containing carboxylic acid functionality;
- each polymer stage is different from any adjacent polymer stage by either about a one percent difference by weight in the amount of any ethylenically unsaturated monomer used therein or by a difference in number average molecular weight between said stage and said adjacent stage of at least about a factor of 2;
- the polymer stages of said particles having a glass transition temperature of about 50° C. or greater comprises at least about 60% by weight of said particles;
- Each of the polymer stages is sequentially emulsion polymerized from a monomer system comprising one or more ethylenically-unsaturated monomers having one or more groups of the formula --HC ⁇ C ⁇ .
- stage refers to the polymer formed during each sequence of polymerization, with the final stage being the last sequence of polymerization and earlier stages being the polymer formed during prior sequences of polymerization.
- ethylenically-unsaturated monomers are styrene, alpha-methylstyrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide methacrylamide, acrylic acid and methacrylic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, and various (C 1 -C 20 )alkyl or (C 3 -C 20 )alkenyl esters of (meth)acrylic acid.
- any of the polymer stages may optionally comprise as one component thereof a small amount of polyethylenically unsaturated monomer, such as ethylene glycol di(meth)acrylate, alyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane trimethacrylate, or divinylbenzene; the proportion thereof being in the range of about 0.1 to 20%, preferable 0.1% to about 3%, by weight based on the total monomer weight of said polymer stage.
- polyethylenically unsaturated monomer such as ethylene glycol di(meth)acrylate, alyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane trimethacrylate, or divinylbenzene
- Each of the polymer stages is different from any immediately adjacent polymer stage by either about a one percent difference by weight in the amount of any ethylenically-unsaturated monomer used therein, or by a difference of at least about a factor of 2in number average molecular weight between said stage and said adjacent stage.
- the polymer stages are distinguishable by either the prescribed monomer difference or the prescribed molecular weight difference or both.
- Each or any stage contains the prescribed amount of one or more of said ethylenically-unsaturated monomers which is not present in the adjacent stage, or the adjacent stage contains the prescribed amount of said ethylenically-unsaturated monomers which is not present in stages immediately adjacent to it, or said adjacent stage contains about one percent more or less of one or more monomers which is present in stages adjacent to it.
- each or any stage has a number average molecular weight which is at least twice or less than one-half that of any adjacent stae.
- Adjacent polymer stage as used herein means a polymer stage which is immediately adjacent and which may be polymerized prior or subsequent to the stage referred to.
- the polymer particles of this invention must contain at least one earlier polymer stage (3) which is prepared from a monomer system which contains less than about 5% by weight of monomer(s) containing carboxylic acid functionality.
- the monomer system for this low-acid polymer stage contains less than 2% of monomer(s) having carboxylic acid functionality.
- High levels of copolymerized carboxylic acid monomers in the earlier stages of these polymer particles have several disadvantages.
- One disadvantage is that the carboxylic acid copolymers are polar and do not adsorb surfactants effectively, thus, making them unstable and prone to coagulation or aggregation into undesirable larger particles.
- the carboxylic acid-containing polymer stages have a high affinity for water which makes them difficult to encapsulate with other polymer stages.
- the present invention has overcome the above disadvantages by using little or no carboxylic acid monomer in this earlier polymer stage.
- the final polymer stage (2) is also emulsion polymerized from a monomer system comprising one or more ethylenically-unsaturated monomer(s) containing one or more --HC ⁇ C ⁇ group(s).
- suitable monomer for the final polymer stage include the same monomers listed above for preparing the other polymer stages and as described in U.S. Pat. No. 4,427,836, which is herein incorporated by reference.
- the specific monomers used and the relative proportions thereof in any final polymer stage formed should be such that the final polymer stage is preferably permeable to bases.
- any other polymer stage which is formed subsequent to said low-acid polymer stage (3) should preferably be permeable to bases to allow the bases to diffuse through to the low-acid polymer stage (3) in the subsequent neutralization step.
- the final polymer stage (2) must have a Tg of about 50° C. or greater, but the Tg of the final polymer stage may be equal to, less than or greater than the Tg of the earlier polymer stages.
- at least one polymer stage which is formed subsequent to said low-acid polymer stage (3) has a higher Tg than said low-acid polymer stage.
- the low-acid polymer stage (3) has a Tg of about 150° C. or less; more preferably about 90° C. or less.
- the low-acid polymer stage (3) preferably has a number average molecular weight of about 10,000 or less.
- the polymer stages having a Tg of about 50° C. or greater cumulatively comprise at least about 60% by weight of the polymer particles.
- the Tg of the polymer stages can be calculated using the Fox equation:
- the first stage of emulsion polymerization in the process of the present invention may be the preparation of a seed polymer consisting of small dispersed polymer particles which are insoluble in the aqueous emulsion polymerization medium.
- This seed polymer provides particles of minute size which form the nuclei on which the subsequent polymer stages are formed.
- a water-soluble, free-radical initiator such as hydrogen peroxide, tert-butyl hydroperoxide, or an alkali metal (sodium, potassium or lithium) or ammonium persulfate or a mixture of such an initiator with a reducing agent (such as a sulfite; more specifically an alkali metal metabisulfite, hydrosulfite, or hyposulfite, or sodium formaldehyde sulfoxylate) to form a redox system.
- a reducing agent such as a sulfite; more specifically an alkali metal metabisulfite, hydrosulfite, or hyposulfite, or sodium formaldehyde sulfoxylate
- the amount of initiator may be from 0.01 to about 2% by weight of the monomer charged and, in a redox system, a corresponding range (0.01 to about 2%) of reducing agent may be used.
- the temperature may be in the range of about 10° C. to 100° C. In the case of the persulfate systems, the temperature is preferably in the range of 60° C. to 90° C. In the redox system, the temperature is preferably in the range of about 30° to 70° C., more preferably about 40° to 70° C., most preferably in the range of about 55° to 70° C.
- the proportion of emulsifier may be zero, but, in the situation wherein a persulfate initiator is used, it can range up to about 5 weight percent, based on the weight of monomer charged to the first stage of polymerization.
- the subsequent stages of polymer-formation deposit the most-recently formed polymer on the existing dispersed polymer particles resulting from the preceding step or stage.
- the amount of emulsifier should be kept between 20% to about 60% of the amount theoretically required to saturate the surface of the polymer particles present in the reaction mixture at any given time as described in U.S. Pat. No. 2,520,959.
- anionic emulsifiers include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyldiphenyloxide disulfonate, nonylphenoxyethylpoly(10)ethoxyethyl sulfate ammonium salt, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate, sodium or ammonium salts of phosphate esters of ethoxylated nonylphenol, sodium octoxynol-3-sulfonate, sodium cocoyl sarcosinate, sodium 1-alkyloxy-2-hydroxypropyl sulfonate, sodium alpha-olefin (C 14 -C 16 ) sulfonate, sulfates of hydroxyalkanols, tetraso
- a subsequent stage or stages of emulsion polymerization is effected to form the final polymer stage on the earlier polymer stages particles. This may be performed in the same reaction vessel in which formation of earlier polymer stages were accomplished or the reaction medium containing the dispersed earlier stage particles may be transferred to another reaction container. It is generally unnecessary to add emulsifier unless a polymodal product is desired.
- the amount of polymer deposited to form the stages of polymer is generally such as to provide an overall size of the multi-stage polymer particle of about 0.07 to about 4.5 microns, preferably about 0.1 to about 3.5 microns, more preferably about 0.2 to about 2.0 microns, in unswollen condition (that is, before any neutralization to raise the pH to about 5 or higher).
- the weight ratio of polymer stages having a Tg of about 50° C. or greater comprises at least about 80% by weight of the complete multi-stage polymer particles.
- the polymer particles are contacted with a non-polymeric compound containing at least one carboxylic acid group for a sufficient period of time to allow the acid-containing compound to be absorbed into the low-acid polymer stage (3).
- the acid-containing compound should be added after adjusting the polymer composition to pH 4 or less to reduce the compound's solubility in the aqueous phase and increase its solubility in the polymer.
- the acid-containing compound has a solubility in water greater than 0.001% and less than about 2% at pH 5 or less and at the Tg of the final polymer stage.
- This solubility range is low enough to allow most of the acid-containing compound to absorb into the low-acid polymer stage, yet high enough so that it can diffuse through the aqueous phase to the polymer particles at a sufficient rate.
- the amount of acid-containing compound to the weight of the complete multi-stage polymer particle ranges fromo about 1:2 to about 1:50.
- the Tg of the neat polymer of the final polymer stage can be lowered during the swelling step to a "plasticized Tg" with a plasticizing solvent to facilitate swelling of the polymer particles upon treatment with base.
- the plasticizing solvent also aids in penetration of the polymer by the base.
- Suitable amounts of plasticizing solvents are about 1 to about 100 parts by weight based on 100 parts by weight of polymer.
- Suitable solvents are any which will plasticize the final polymer stage; for example, hexanol, ethanol, 3-hydroxy-2,2,4-trimethylpentyl isobutyrate, toluene, and the like and mixtures thereof.
- the solvent can be added either before, after or with the addition of the base. In certain causes the monomer system itself can function as the plasticizing solvent for the polymer.
- the multi-stage polymer particle dispersions of the present invention are useful in aqueous coating and impregnating compositions as opacifying agents in such compositions. They are usefuleither as a supplement to, or replacement of, pigmentary matter and/or extenders therefor.
- the aqueous dispersons of the multi-stage polymer particles may be added directly to the coating and/or impregnating compositions.
- the multi-stage polymer particles may be isolated fromt he dispersions and dried to make them free-flowing in character so that they can be packaged, sold and shipped or stored before use.
- the dry powder thus obtained can also be used in coatings based or organic solvents provided the final polymer stage of the multi-stage polymer particles is not soluble in the organic solvent.
- a 3-liter, round-bottomed flask with 4 necks was fitted with reflux condenser, paddle stirrer, thermometer and nitrogen inlet. 1500 grams of deionized water were added to the flask and stirred under a nitrogen atmosphere at 85° C. To the deionized water were added 3 grams of sodium persulfate and 40 grams of an acrylic seed latex having a 46.5% solids content and an average diameter of 95 nanometers.
- a monomer emulsion 140 g. of water, 6 g. of 23% sodium dodecybenzenesulfonic acid, 360 g. of isobutyl methacrylate and 40 g.
- the resultant latex was held at 85° C. for 30 minutes, cooled and filtered.
- the resultant low-acid stage polymer latex had an 18.7% solid content, average particle diameter of 260 nanometers and a number average molecular weight of 2000 as measured by gel permeation chromatography.
- Example 2 To 470 g. of deionized water, stirred under nitrogen in a flask equipped as in Example 1, was added 50 g. of the low-acid stage polymer latex from Example 1 along with 20 g. of benzoic acid. The mixture in the flask was heated to 80° C. and then 1.2 g. of sodium persulfate dissolved in 10 g. of water was added. A monomer mixture of 46 g. of butyl methacrylate, 66.7 g. of methyl methacrylate and 2.3 g. of methacrylic acid was added slowly over a one-hour period to give a second polymer stage. After a 10-minute hold at 80° C. to complete the polymerization, 115 g.
- Multi-stage polymer particles were prepared following the procedures of Example II, except that the benzoic acid was mixed with styrene and this mixture was added to the flask over a one-hour period.
- the resulting latex product had a 28.3% solids content, pH of 9.9 and S/mil of 0.16. Voids were noticeable in the dry polymer particles through examination under a microscope.
- Multi-stage polymer particles were prepared following the procedures of Example II, except that the benzoic acid was added to the flask immediately after addition of the styrene was complete. When the ammonia was added, the latex became thick and 100 grams of water were added. The resulting latex product had a 23.3% solids content, pH of 9.7 and S/mil of 0.13. Examination of dry polymer particles under a microscope showed a single void in each particle.
- a low molecular weight, earlier stage latex was prepared following the procedures of Example I, except that 50 grams of an acrylic latex seed (41.3% solids, average diameter 57 nm(were used and isobutyl methacrylate was replaced with an equal amount of butyl methacrylate.
- the resulting latex has an 18.8% solids content and an average particles diameter of 150 nm.
- This earlier stage latex as then used to prepare multi-stage polymer particles following the procedures of Example II, except that the amount of initial deionized water was increased to 700 grams and benzoic acid was replaced with azelaic acid.
- the resulting multi-stage latex product had a 23.8% solids conotent, pH of 9.4, average particle diameter of 470 nm, and S/mil of 0.20.
- This earlier stage latex waqs then used to prepare multi-stage polymer following the procedures of Example V.
- the resulting multi-stage latex product had a 24.4% solids content, pH of 9.2, average particle diameter of 482 nm, and S/mil of 0.15.
- Multi-stage polymer particles were prepared following the procedures of Example VI,e xcept that butyl methacrylate in the earlier stage was replaced with an equal amount of butyl acrylate.
- the resulting multi-stae latex product had a 23.4% solids content, pH of 9.4, average particle diameter of 503 nm and S/mil of 0.11.
- Multi-stage polymer particles were prepared following the procedures of Example V, except that butyl methacrylate in the earlier stage was replaced with an equal amount of styrene.
- the resulting multi-stage latex product had a 24.1% solids content, pH of 9.3, average particle diameter of 389 nm, and S/mil of 0.11.
- the earlier polymer stage had a measured Tg of 70° C. by differential scanning calorimetry.
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Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/197,063 US4880842A (en) | 1988-05-20 | 1988-05-20 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
CA000599026A CA1303438C (fr) | 1988-05-20 | 1989-05-08 | Particules de polymeres s'opacifiant a plusieurs degres, contenant un acide non polymerique qui y est abosrbe |
PH38632A PH25322A (en) | 1988-05-20 | 1989-05-10 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbent therein |
MX16000A MX164012B (es) | 1988-05-20 | 1989-05-11 | Particulas de polimero opacificadoras,de etapas multiples,que contienen absorbido acido no polimerico |
IE156189A IE64597B1 (en) | 1988-05-20 | 1989-05-12 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
NZ229145A NZ229145A (en) | 1988-05-20 | 1989-05-16 | Manufacture of multi-stage polymer particles containing a carboxylic acid compound, which are induced to swell, forming voids within the particles |
AT89304964T ATE91491T1 (de) | 1988-05-20 | 1989-05-17 | Mehrstufige opazifierende polymerpartikel mit absorbierter nichtpolymerisierbarer saeure. |
EP89304964A EP0342944B1 (fr) | 1988-05-20 | 1989-05-17 | Particules de polymère à plusieurs étapes rendant opaque, contenant de l'acide non polymérisable absorbé |
AU34868/89A AU616756B2 (en) | 1988-05-20 | 1989-05-17 | Multi-stage opacifying polymer particles containing non- polymeric acid absorbed therein |
DE89304964T DE68907521T2 (de) | 1988-05-20 | 1989-05-17 | Mehrstufige opazifierende Polymerpartikel mit absorbierter nichtpolymerisierbarer Säure. |
ES89304964T ES2058519T3 (es) | 1988-05-20 | 1989-05-17 | Particulas de polimero opacificantes multi-fase que contienen acido no polimerico absorbido en las mismas. |
BR898902330A BR8902330A (pt) | 1988-05-20 | 1989-05-18 | Processo para preparacao de particulas opacificantes de polimero de multiplos estagios |
NO891978A NO173391C (no) | 1988-05-20 | 1989-05-18 | Fremgangsm}te til fremstilling av opasitets!kende polymerpartikler, og anvendelse av disse i beleggsmateriale |
DK244989A DK244989A (da) | 1988-05-20 | 1989-05-19 | Fremgangsmaade til fremstilling af flertrinspolymerpartikler indeholdende absorberet ikke-polymer syre |
KR1019890006753A KR0158367B1 (ko) | 1988-05-20 | 1989-05-19 | 멀티스테이지 중합체 입자 및 그 제조 방법 |
FI892446A FI93017C (fi) | 1988-05-20 | 1989-05-19 | Menetelmä opasifioivien monikerrospolymeerihiukkasten valmistamiseksi sekä näitä hiukkasia sisältävä päällystekoostumus |
IL90355A IL90355A (en) | 1988-05-20 | 1989-05-19 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
JP1124580A JP2774145B2 (ja) | 1988-05-20 | 1989-05-19 | 多層不透明化重合体粒子の製造方法および該粒子を含有するコーティング組成物 |
CN89103403A CN1032013C (zh) | 1988-05-20 | 1989-05-20 | 制备不透明的内含一个或多个空隙聚合物颗粒的方法 |
US07/382,612 US4970241A (en) | 1988-05-20 | 1989-07-19 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
SG103593A SG103593G (en) | 1988-05-20 | 1993-09-09 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
HK1230/93A HK123093A (en) | 1988-05-20 | 1993-11-11 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/197,063 US4880842A (en) | 1988-05-20 | 1988-05-20 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/382,612 Continuation-In-Part US4970241A (en) | 1988-05-20 | 1989-07-19 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
Publications (1)
Publication Number | Publication Date |
---|---|
US4880842A true US4880842A (en) | 1989-11-14 |
Family
ID=22727887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/197,063 Expired - Lifetime US4880842A (en) | 1988-05-20 | 1988-05-20 | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
Country Status (20)
Country | Link |
---|---|
US (1) | US4880842A (fr) |
EP (1) | EP0342944B1 (fr) |
JP (1) | JP2774145B2 (fr) |
KR (1) | KR0158367B1 (fr) |
CN (1) | CN1032013C (fr) |
AT (1) | ATE91491T1 (fr) |
AU (1) | AU616756B2 (fr) |
BR (1) | BR8902330A (fr) |
CA (1) | CA1303438C (fr) |
DE (1) | DE68907521T2 (fr) |
DK (1) | DK244989A (fr) |
ES (1) | ES2058519T3 (fr) |
FI (1) | FI93017C (fr) |
HK (1) | HK123093A (fr) |
IE (1) | IE64597B1 (fr) |
IL (1) | IL90355A (fr) |
MX (1) | MX164012B (fr) |
NO (1) | NO173391C (fr) |
NZ (1) | NZ229145A (fr) |
PH (1) | PH25322A (fr) |
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US5273824A (en) * | 1990-02-03 | 1993-12-28 | Mitsui Toatsu Chemicals, Incorporated | Cored multi-shell emulsion particle |
WO1994004603A1 (fr) * | 1992-08-19 | 1994-03-03 | The Dow Chemical Company | Particules creuses de latex polymere |
WO1994020653A1 (fr) * | 1993-03-02 | 1994-09-15 | Courtaulds Plc | Fibre |
EP0696602A1 (fr) | 1994-08-12 | 1996-02-14 | Rohm And Haas Company | Polymères hydrophiles encapsulés et leur préparation |
US5521253A (en) * | 1990-10-12 | 1996-05-28 | The Dow Chemical Company | Hollow polymer latex particles |
US5525639A (en) * | 1993-04-27 | 1996-06-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Expanded foamed bead of a rubber-modified styrene polymer |
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FR3105028B1 (fr) * | 2019-12-23 | 2022-09-23 | Cromology | Procédé d’application d’une peinture substantiellement exempte de dioxyde de titane |
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Cited By (117)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4972000A (en) * | 1988-02-29 | 1990-11-20 | Japan Synthetic Rubber Co., Ltd. | Hollow polymer particles, process for production thereof, and use thereof as pigment |
US5273824A (en) * | 1990-02-03 | 1993-12-28 | Mitsui Toatsu Chemicals, Incorporated | Cored multi-shell emulsion particle |
US5521253A (en) * | 1990-10-12 | 1996-05-28 | The Dow Chemical Company | Hollow polymer latex particles |
US5157084A (en) * | 1990-10-12 | 1992-10-20 | The Dow Chemical Company | Process of making hollow polymer latex particles |
US5135568A (en) * | 1991-01-30 | 1992-08-04 | Rohm And Haas Company | Method for improving fluorescent coatings |
US5536771A (en) * | 1991-08-15 | 1996-07-16 | Nippon Paint Co., Ltd. | Aqueous crosslinked polymer particles and their production |
US5639805A (en) * | 1991-12-13 | 1997-06-17 | Korea Chemical Co., Ltd. | Process for preparing core-shell emulsion polymer particles and resulting product containing such particles |
US5527613A (en) * | 1992-04-10 | 1996-06-18 | Rohm And Haas Company | Synthesis of latex capsules |
SG84480A1 (en) * | 1992-04-10 | 2001-11-20 | Rohm & Haas | Polymeric particles |
WO1994004603A1 (fr) * | 1992-08-19 | 1994-03-03 | The Dow Chemical Company | Particules creuses de latex polymere |
WO1994020653A1 (fr) * | 1993-03-02 | 1994-09-15 | Courtaulds Plc | Fibre |
US5609957A (en) * | 1993-03-02 | 1997-03-11 | Courtaulds Plc | Fiber |
US5635543A (en) * | 1993-04-27 | 1997-06-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Expanded foamed bead of a rubber-modified styrene polymer |
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Also Published As
Publication number | Publication date |
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FI892446A0 (fi) | 1989-05-19 |
PH25322A (en) | 1991-04-30 |
KR900018144A (ko) | 1990-12-20 |
DE68907521D1 (de) | 1993-08-19 |
CN1032013C (zh) | 1996-06-12 |
DE68907521T2 (de) | 1993-12-02 |
BR8902330A (pt) | 1990-01-09 |
NZ229145A (en) | 1991-12-23 |
FI892446A (fi) | 1989-11-21 |
NO891978L (no) | 1989-11-21 |
IL90355A (en) | 1992-12-01 |
NO173391B (no) | 1993-08-30 |
EP0342944A2 (fr) | 1989-11-23 |
JP2774145B2 (ja) | 1998-07-09 |
IE891561L (en) | 1989-11-20 |
CA1303438C (fr) | 1992-06-16 |
DK244989D0 (da) | 1989-05-19 |
HK123093A (en) | 1993-11-19 |
NO891978D0 (no) | 1989-05-18 |
JPH0264103A (ja) | 1990-03-05 |
EP0342944B1 (fr) | 1993-07-14 |
NO173391C (no) | 1993-12-08 |
FI93017C (fi) | 1995-02-10 |
ATE91491T1 (de) | 1993-07-15 |
EP0342944A3 (en) | 1990-05-09 |
FI93017B (fi) | 1994-10-31 |
KR0158367B1 (ko) | 1999-01-15 |
DK244989A (da) | 1989-11-21 |
AU3486889A (en) | 1989-11-23 |
AU616756B2 (en) | 1991-11-07 |
ES2058519T3 (es) | 1994-11-01 |
IL90355A0 (en) | 1989-12-15 |
CN1040039A (zh) | 1990-02-28 |
MX164012B (es) | 1992-07-09 |
IE64597B1 (en) | 1995-08-23 |
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